The present state of research on the structure of amorphous silicon monoxide (SiO) is reviewed. The black, coal-like modification of bulk SiO is studied by a combination of diffraction, microscopy, spectroscopy, and magnetometry methods. Partial radial distribution functions of SiO are obtained by X-ray, neutron and electron diffraction. Disproportionation of SiO into Si and SiO2 is verified. High resolution TEM gives an upper limit of less than 2 nm for the typical Si cluster size. The Si K-edge electron energy-loss near-edge structure (ELNES) data of SiO are interpreted in terms of the oxidation states Si4+ and Si0. X-ray photoelectron spectroscopy gives first details about possible stoichiometric inhomogeneities related to internal interfaces. The wipe-out effect in the 29Si MAS NMR signal of SiO is confirmed experimentally. The new estimation of the wipe-out radius is about 1.1 nm. First-time W-band, Q-band, and X-band ESR and SQUID measurements indicate an interfacial defect structure. Frequency distributions of atomic nearest-neighbours are derived. The interface clusters mixture model (ICM model) suggested here describes the SiO structure as a disproportionation in the initial state. The model implies clusters of silicon dioxide and clusters of silicon surrounded by a sub-oxide matrix that is comparable to the well-known thin Si/SiO2 interface and significant in the volume because of small cluster sizes.

An interface clusters mixture model for the structure of amorphous silicon monoxide (SiO)

Silicon‐rich SiO2 films of various compositions were deposited by atmospheric or plasma‐enhanced chemical vapor deposition (CVD) techniques. These films were annealed at various temperatures between 700 and 1100 °C. The growth and crystallinity of the silicon clusters were monitored by transmission electron microscopy. The growth of the silicon clusters was found to be diffusion controlled with an activation energy measured to a first approximation at 1.9 eV/atom for both atmospheric and plasma‐enhanced CVD films. A minimum annealing temperature of between 800 and 950 °C and a minimum amount of excess Si above SiO2 are required to form crystalline silicon particles in the films. The minimum silicon crystal diameter was measured at 2.5 nm.

Annealing characteristics of Si‐rich SiO2 films

Infrared absorption spectra and compositions of evaporated silicon oxides (SiOx)

Optical interference fringe measurements of the thickness of transparent layers can be rapid, accurate, and nondestructive. If the refractive index n of the layer being measured is known, it may be combined directly with interference fringe information to yield the layer thickness t. If, however, n is unknown, the measurement procedure necessarily becomes more complicated. In this paper, a new and simpler optical interference method is presented for the approximate determination of both n and t of a transparent layer on a transparent substrate. The required experimental information is obtained from a single spectrophotometric recording of either the reflectance or transmittance of the layer and its substrate. The theory of the method is presented, and an application of the method to measurements of layers of SIPOS (Semi-Insulating POlycrystalline Silicon) is described. The method requires that the layer being measured must be uniformly deposited on a flat substrate, and it must neither absorb nor scatter the light passing through it. The major approximation inherent in the method is that both the layer and the substrate are assumed to be nondispersive over the wavelength region of interest.

Optical interference method for the approximate determination of refractive index and thickness of a transparent layer

Thermally deposited silicon films doped with oxygen atoms and used as passivation films on silicon devices have been studied with transmission electron microscopy, x‐ray diffraction, and ESCA. The films contain at least two phases, silicon microcrystals and silicon oxide. The size of the microcrystals in as‐deposited films was dependent both on the deposition temperature and on the oxygen concentration. Heat treatment caused crystal growth which depended mainly on the annealing temperature and weakly on the annealing time. The lattice constant of the microcrystals was directly related to their size. The silicon oxide phase in as‐deposited films was found to be SiO1.4. The results suggest ’’mosaic’’ model of the films which are amorphous when the diameter of the silicon microcrystals was less than 10 A.

T. Adachi

Papers

Crystallographic study of semi‐insulating polycrystalline silicon (SIPOS) doped with oxygen atoms

Electronic properties of Semi-Insulating Polycrystalline-Silicon (SIPOS) doped with oxygen atoms